U.S. patent application number 17/522331 was filed with the patent office on 2022-05-26 for solid-state bipolar battery having thick electrodes.
This patent application is currently assigned to GM GLOBAL TECHNOLOGY OPERATIONS LLC. The applicant listed for this patent is GM GLOBAL TECHNOLOGY OPERATIONS LLC. Invention is credited to Mei CAI, Zhe LI, Haijing LIU, Yong LU, Xiaochao QUE, Meiyuan WU, Thomas A. YERSAK.
Application Number | 20220166031 17/522331 |
Document ID | / |
Family ID | |
Filed Date | 2022-05-26 |
United States Patent
Application |
20220166031 |
Kind Code |
A1 |
LI; Zhe ; et al. |
May 26, 2022 |
SOLID-STATE BIPOLAR BATTERY HAVING THICK ELECTRODES
Abstract
The present disclosure provides a solid-state bipolar battery
that includes negative and positive electrodes having thicknesses
between about 100 .mu.m and about 3000 .mu.m, and a solid-state
electrolyte layer disposed between the negative electrode and the
positive electrode and having a thickness between about 5 .mu.m and
about 100 .mu.m. The first electrode includes a plurality of
negative solid-state electroactive particles embedded on or
disposed within a first porous material. The second electrode
includes plurality of positive solid-state electroactive particles
embedded on or disposed within a second porous material that is the
same or different from the first porous material. The solid-state
bipolar battery includes a first current collector foil disposed on
the first porous material, and a second current collector foil
disposed on the second porous material. The first and second
current collector foils may each have a thickness less than or
equal to about 10 .mu.m.
Inventors: |
LI; Zhe; (Shanghai, CN)
; QUE; Xiaochao; (Shanghai, CN) ; LIU;
Haijing; (Shanghai, CN) ; LU; Yong; (Shanghai,
CN) ; WU; Meiyuan; (Shanghai, CN) ; YERSAK;
Thomas A.; (Royal Oak, MI) ; CAI; Mei;
(Bloomfield Hills, MI) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
GM GLOBAL TECHNOLOGY OPERATIONS LLC |
Detroit |
MI |
US |
|
|
Assignee: |
GM GLOBAL TECHNOLOGY OPERATIONS
LLC
Detroit
MI
|
Appl. No.: |
17/522331 |
Filed: |
November 9, 2021 |
International
Class: |
H01M 4/80 20060101
H01M004/80 |
Foreign Application Data
Date |
Code |
Application Number |
Nov 24, 2020 |
CN |
202011327145.4 |
Claims
1. A solid-state battery comprising: a first electrode having a
thickness greater than or equal to about 100 .mu.m to less than or
equal to about 3000 .mu.m and comprising a plurality of first
solid-state electroactive particles; a second electrode having a
thickness greater than or equal to about 100 .mu.m to less than or
equal to about 3000 .mu.m and comprising a plurality of second
solid-state electroactive particles, wherein the plurality of
second solid-state electroactive particles are embedded on or
disposed within a porous material; and a solid-state electrolyte
layer disposed between the first electrode and the second
electrode.
2. The solid-state battery of claim 1, wherein the porous material
has a porosity greater than or equal to about 80 vol. % to less
than or equal to about 95 vol. %, an average pore size greater than
or equal to about 2 .mu.m to less than or equal to about 1000
.mu.m, and a thickness greater than or equal to about 100 .mu.m to
less than or equal to about 4000 .mu.m.
3. The solid-state battery of claim 1, wherein the porous material
is a metal foam selected from an aluminum (Al) foam, a nickel (Ni)
foam, a copper (Cu) foam, a nickel-chromium (Ni--Cr) foam, a
nickel-tin (Ni--Sn) foam, and a titanium (Ti) foam.
4. The solid-state battery of claim 1, wherein the porous material
is one of a carbon nanofiber three-dimensional foam, a graphene
foam, a carbon cloth, a carbon fiber-embedded carbon nanotubes, and
a graphene-nickel foam.
5. The solid-state battery of claim 1, wherein the porous material
is a first porous material, and wherein the first electrode has a
thickness greater than or equal to about 500 .mu.m to less than or
equal to about 3000 .mu.m, and the plurality of first solid-state
electroactive particles are embedded on or disposed within a second
porous material, wherein the first and second porous materials are
the same or different.
6. The solid-state battery of claim 5, wherein the solid-state
electrolyte layer comprises a plurality of solid-state electrolyte
particles.
7. The solid-state battery of claim 6, wherein the plurality of
solid-state electrolyte particles is a first plurality of
solid-state electrolyte particles, the first electrode further
comprises a second plurality of solid-state electrolyte particles
embedded on or disposed within the first porous material with the
first plurality of solid-state electroactive particles, and the
second electrode further comprises a third plurality of solid-state
electrolyte particles embedded on or disposed within the second
porous material with the second plurality of solid-state
electroactive particles, wherein the first, second, and third
pluralities of solid-state electrolyte particles are the same or
different.
8. The solid-state battery of claim 6, wherein the solid-state
electrolyte layer comprises: a first sublayer comprising a first
plurality of solid-state electrolyte particles, and a second
sublayer comprising a second plurality of solid-state electrolyte
particles, wherein the first and second sublayers are the same or
different.
9. The solid-state battery of claim 6, further comprising: a first
current collector foil disposed on the first porous material
adjacent to the first plurality of solid-state electroactive
particles; and a second current collector foil disposed on the
second porous material adjacent the second plurality of solid-state
electroactive particles, wherein each foil has a thickness greater
than or equal to about 2 .mu.m to less than or equal to about 30
.mu.m.
10. The solid-state battery of claim 9, wherein each foil has a
thickness less than about 10 .mu.m.
11. The solid-state battery of claim 9, wherein at least one of the
first and second current collector foils comprises: a first half
comprising a first material, and a second half comprising a second
material, wherein the second half is substantially parallel with
the first half, and the first and second materials are
different.
12. The solid-state battery of claim 1, wherein the solid-state
electrolyte layer has a thickness greater than or equal to about 5
.mu.m to less than or equal to about 100 .mu.m.
13. The solid-state battery of claim 1, wherein the solid-state
battery is a bipolar battery.
14. A solid-state battery comprising: a negative electrode having a
thickness greater than or equal to about 100 .mu.m to less than or
equal to about 3000 .mu.m and comprising a plurality of negative
solid-state electroactive particles embedded on or disposed within
a first porous material; a positive electrode having a thickness
greater than or equal to about 100 .mu.m to less than or equal to
about 3000 .mu.m and comprising a plurality of positive solid-state
electroactive particles embedded on or disposed within a second
porous material, wherein the second porous material is the same or
different from the first porous material; and a solid-state
electrolyte layer disposed between the negative electrode and the
positive electrode, wherein the solid-state electrolyte layer has a
thickness greater than or equal to about 5 .mu.m to less than or
equal to about 100 .mu.m.
15. The solid-state battery of claim 14, wherein the first and
second porous materials each have a porosity greater than or equal
to about 80 vol. % to less than or equal to about 95 vol. %, an
average pore size greater than or equal to about 2 .mu.m to less
than or equal to about 1000 .mu.m, and a thickness greater than or
equal to about 100 .mu.m to less than or equal to about 4000
.mu.m.
16. The solid-state battery of claim 14, wherein the first and
second porous materials each comprise one of an aluminum (Al) foam,
a nickel (Ni) foam, a copper (Cu) foam, a nickel-chromium (Ni--Cr)
foam, a nickel-tin (Ni--Sn) foam, a titanium (Ti) foam, a carbon
nanofiber three-dimensional foam, a graphene foam, a carbon cloth,
a carbon fiber-embedded carbon nanotubes, and a graphene-nickel
foam.
17. The solid-state battery of claim 14, wherein the solid-state
electrolyte layer comprises: a first sublayer comprising a first
plurality of solid-state electrolyte particles, and a second
sublayer comprising a second plurality of solid-state electrolyte
particles, wherein the first and second sublayers are the same or
different.
18. The solid-state battery of claim 14, further comprising: a
first current collector foil disposed on the first porous material
adjacent to the negative solid-state electroactive particles; and a
second current collector foil disposed on the second porous
material adjacent to the positive solid-state electroactive
particles, wherein each foil has a thickness greater than or equal
to about 2 .mu.m to less than or equal to about 30 .mu.m.
19. The solid-state battery of claim 18, wherein at least one of
the first and second current collector foils comprises: a first
half comprising a first material, and a second half comprising a
second material, wherein the second half is substantially parallel
with the first half, and the first and second materials
different.
20. A solid-state bipolar battery comprising: a negative electrode
having a thickness greater than or equal to about 100 .mu.m to less
than or equal to about 3000 .mu.m and comprising a plurality of
negative solid-state electroactive particles embedded on or
disposed within a first porous material; a positive electrode
having a thickness greater than or equal to about 100 .mu.m to less
than or equal to about 3000 .mu.m and comprising a plurality of
positive solid-state electroactive particles embedded on or
disposed within a second porous material, wherein the second porous
material is the same or different from the first porous material
and the first and second porous materials each comprise one of an
aluminum (Al) foam, a nickel (Ni) foam, a copper (Cu) foam, a
nickel-chromium (Ni--Cr) foam, a nickel-tin (Ni--Sn) foam, a
titanium (Ti) foam, a carbon nanofiber three-dimensional foam, a
graphene foam, a carbon cloth, a carbon fiber-embedded carbon
nanotubes, and a graphene-nickel foam; a solid-state electrolyte
layer comprising a plurality of solid-state electrolyte particles
disposed between the negative electrode and the positive electrode,
wherein the solid-state electrolyte layer has a thickness greater
than or equal to about 5 .mu.m to less than or equal to about 100
.mu.m; a first current collector foil disposed on the first porous
material adjacent to the negative solid-state electroactive
particles; and a second current collector foil disposed on the
second porous material adjacent to the positive solid-state
electroactive particles, wherein the first and second current
collector foils each has a thickness less than or equal to about 10
.mu.m.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit and priority of Chinese
Application No. 202011327145.4, filed Nov. 24, 2020. The entire
disclosure of the above application is incorporated herein by
reference.
INTRODUCTION
[0002] This section provides background information related to the
present disclosure which is not necessarily prior art.
[0003] Electrochemical energy storage devices, such as lithium-ion
batteries, can be used in a variety of products, including
automotive products such as start-stop systems (e.g., 12V
start-stop systems), battery-assisted systems (".mu.BAS"), Hybrid
Electric Vehicles ("HEVs"), and Electric Vehicles ("EVs"). Typical
lithium-ion batteries include two electrodes and an electrolyte
component and/or separator. One of the two electrodes can serve as
a positive electrode or cathode, and the other electrode can serve
as a negative electrode or anode. Lithium-ion batteries may also
include various terminal and packaging materials. Rechargeable
lithium-ion batteries operate by reversibly passing lithium ions
back and forth between the negative electrode and the positive
electrode. For example, lithium ions may move from the positive
electrode to the negative electrode during charging of the battery
and in the opposite direction when discharging the battery. A
separator and/or electrolyte layer may be disposed between the
negative and positive electrodes. The electrolyte is suitable for
conducting lithium ions between the electrodes and, like the two
electrodes, may be in a solid form, a liquid form, or a
solid-liquid hybrid form. In the instances of solid-state
batteries, which include a solid-state electrolyte layer disposed
between solid-state electrodes, the solid-state electrolyte
physically separates the solid-state electrodes so that a distinct
separator is not required.
[0004] Solid-state batteries have advantages over batteries that
include a separator and a liquid organic electrolyte. These
advantages can include a longer shelf life with lower
self-discharge, simpler thermal management, a reduced need for
packaging, and the ability to operate within a wider temperature
window. For example, solid-state electrolytes are generally
non-volatile and non-flammable, so as to allow cells to be cycled
under harsher conditions without experiencing diminished potential
or thermal runaway, which can potentially occur with the use of
liquid electrolytes. However, solid-state batteries generally
experience comparatively low power capabilities, for example, as a
result of poor electron and ion transport within the electrodes,
which may be caused by limited contact, or void spaces, between
solid-state active particles and/or solid-state electrolyte
particles. Solid-state batteries may also have comparatively thin
electrodes with lower active material loadings (e.g., <70 wt. %)
resulting in limited energy densities, for example low energy
densities (e.g., <190 Wh/Kg). Such results occur because it is
often difficult to build a good electron conductive network when
the electrode is thick while the amount of solid-state electrolyte
that needs to be added to the electrode to obtain sufficient ionic
contact is often large. Accordingly, it would be desirable to
develop high-performance solid-state battery designs, materials,
and methods that improve power capabilities, as well as energy
density.
SUMMARY
[0005] This section provides a general summary of the disclosure,
and is not a comprehensive disclosure of its full scope or all of
its features.
[0006] The present disclosure relates to solid-state batteries
(SSBs), for example bipolar solid-state batteries, that include a
metal foam material, for example as a current collector. Each
bipolar solid-state battery includes a plurality of solid-state
electroactive material particles and/or solid-state electrolyte
particles embedded within pores of a metal foam and one or more
current collector foils disposed on or adjacent to one or more
surfaces of the metal foam material.
[0007] In various aspects, the present disclosure provides a
solid-state battery that includes a first electrode having a
thickness greater than or equal to about 100 .mu.m to less than or
equal to about 3000 .mu.m; a second electrode having a thickness
greater than or equal to about 100 .mu.m to less than or equal to
about 3000 .mu.m; and a solid-state electrolyte layer disposed
between the first electrode and the second electrode. The first
electrode includes a plurality of first solid-state electroactive
particles. The second electrode includes a plurality of second
solid-state electroactive particles and the plurality of second
solid-state electroactive particles are embedded on or disposed
within a porous material.
[0008] In one aspect, the porous material may have a porosity
greater than or equal to about 80 vol. % to less than or equal to
about 95 vol. %, an average pore size greater than or equal to
about 2 .mu.m to less than or equal to about 1000 .mu.m, and a
thickness greater than or equal to about 100 .mu.m to less than or
equal to about 4000 .mu.m.
[0009] In one aspect, the porous material may be a metal foam
selected from an aluminum (Al) foam, a nickel (Ni) foam, a copper
(Cu) foam, a nickel-chromium (Ni--Cr) foam, a nickel-tin (Ni--Sn)
foam, and a titanium (Ti) foam.
[0010] In one aspect, the porous material may be one of a carbon
nanofiber three-dimensional foam, a graphene foam, a carbon cloth,
a carbon fiber-embedded carbon nanotubes, and a graphene-nickel
foam.
[0011] In one aspect, the porous material may be a first porous
material, the first electrode may have a thickness greater than or
equal to about 500 .mu.m to less than or equal to about 3000 .mu.m,
and the plurality of first solid-state electroactive particles may
be embedded on or disposed within a second porous material. The
first and second porous materials may be the same or different.
[0012] In one aspect, the solid-state electrolyte layer may include
a plurality of solid-state electrolyte particles.
[0013] In one aspect, the plurality of solid-state electrolyte
particles may be a first plurality of solid-state electrolyte
particles, the first electrode may further include a second
plurality of solid-state electrolyte particles embedded on or
disposed within the first porous material with the first plurality
of solid-state electroactive particles, and the second electrode
may further include a third plurality of solid-state electrolyte
particles embedded on or disposed within the second porous material
with the second plurality of solid-state electroactive particles.
The first, second, and third pluralities of solid-state electrolyte
particles may be the same or different.
[0014] In one aspect, the solid-state electrolyte layer includes a
first sublayer including a first plurality of solid-state
electrolyte particles, and a second sublayer including a second
plurality of solid-state electrolyte particles. The first and
second sublayers may be the same or different.
[0015] In one aspect, the solid-state battery further includes a
first current collector foil disposed on the first porous material
adjacent to the first plurality of solid-state electroactive
particles, and a second current collector foil disposed on the
second porous material adjacent to the second plurality of
solid-state electroactive particles. Each foil may have a thickness
greater than or equal to about 2 .mu.m to less than or equal to
about 30 .mu.m.
[0016] In one aspect, each foil has a thickness less than about 10
.mu.m.
[0017] In one aspect, at least one of the first and second current
collector foils includes a first half that includes a first
material, and a second half that includes a second material. The
second half may be substantially parallel with the first half. The
first and second materials may be different.
[0018] In one aspect, the solid-state electrolyte layer may have a
thickness greater than or equal to about 5 .mu.m to less than or
equal to about 100 .mu.m.
[0019] In one aspect, the solid-state battery is a bipolar
battery.
[0020] In various other aspects, the present disclosure provides a
solid-state battery that includes a negative electrode having a
thickness greater than or equal to about 100 .mu.m to less than or
equal to about 3000 .mu.m, a positive electrode having a thickness
greater than or equal to about 100 .mu.m to less than or equal to
about 3000 .mu.m, and a solid-state electrolyte layer disposed
between the negative electrode and the positive electrode. The
first electrode may include a plurality of negative solid-state
electroactive particles embedded on or disposed within a first
porous material. The second electrode may include a plurality of
positive solid-state electroactive particles embedded on or
disposed within a second porous material. The second porous
material may be the same or different from the first porous
material. The solid-state electrolyte layer may have a thickness
greater than or equal to about 5 .mu.m to less than or equal to
about 100 .mu.m.
[0021] In one aspect, the first and second porous materials may
each have a porosity greater than or equal to about 80 vol. % to
less than or equal to about 95 vol. %, an average pore size greater
than or equal to about 2 .mu.m to less than or equal to about 1000
.mu.m, and a thickness greater than or equal to about 100 .mu.m to
less than or equal to about 4000 .mu.m.
[0022] In one aspect, the first and second porous materials each
include one of an aluminum (Al) foam, a nickel (Ni) foam, a copper
(Cu) foam, a nickel-chromium (Ni--Cr) foam, a nickel-tin (Ni--Sn)
foam, a titanium (Ti) foam, a carbon nanofiber three-dimensional
foam, a graphene foam, a carbon cloth, a carbon fiber-embedded
carbon nanotube, and a graphene-nickel foam.
[0023] In one aspect, the solid-state electrolyte layer includes a
first sublayer including a first plurality of solid-state
electrolyte particles, and a second sublayer including a second
plurality of solid-state electrolyte particles. The first and
second sublayers may be the same or different.
[0024] In one aspect, the solid-state battery further includes a
first current collector foil disposed on the first porous material
adjacent to the negative solid-state electroactive particle, and a
second current collector foil disposed on the second porous
material adjacent to the positive solid-state electroactive
particles. Each foil may have a thickness greater than or equal to
about 2 .mu.m to less than or equal to about 30 .mu.m.
[0025] In one aspect, at least one of the first and second current
collector foils includes a first half including a first material,
and a second half including a second material. The second half may
be substantially parallel with the first half. The first and second
materials may be different.
[0026] In one aspect, the solid-state battery is a bipolar
battery.
[0027] In various aspects, the present disclosure provides a
solid-state bipolar battery that includes a negative electrode
having a thickness greater than or equal to about 100 .mu.m to less
than or equal to about 3000 .mu.m, a positive electrode having a
thickness greater than or equal to about 100 .mu.m to less than or
equal to about 3000 .mu.m, and a solid-state electrolyte layer
including a plurality of solid-state electrolyte particles disposed
between the negative electrode and the positive electrode and
having a thickness greater than or equal to about 5 .mu.m to less
than or equal to about 100 .mu.m. The first electrode includes a
plurality of negative solid-state electroactive particles embedded
on or disposed within a first porous material. The second electrode
includes a plurality of positive solid-state electroactive
particles embedded on or disposed within a second porous material.
The second porous material may be the same or different from the
first porous material. The first and second porous materials may
each include one of an aluminum (Al) foam, a nickel (Ni) foam, a
copper (Cu) foam, a nickel-chromium (Ni--Cr) foam, a nickel-tin
(Ni--Sn) foam, a titanium (Ti) foam, a carbon nanofiber
three-dimensional foam, a graphene foam, a carbon cloth, a carbon
fiber-embedded carbon nanotube, and a graphene-nickel foam. The
solid-state bipolar battery may further include a first current
collector foil disposed on the first porous material adjacent to
the negative solid-state electroactive particles, and a second
current collector foil disposed on the second porous material
adjacent to the positive solid-state electroactive particles. The
first and second current collector foils may each have a thickness
less than or equal to about 10 .mu.m.
[0028] Further areas of applicability will become apparent from the
description provided herein. The description and specific examples
in this summary are intended for purposes of illustration only and
are not intended to limit the scope of the present disclosure.
BRIEF DESCRIPTION OF THE DRAWINGS
[0029] The drawings described herein are for illustrative purposes
only of selected embodiments and not all possible implementations,
and are not intended to limit the scope of the present
disclosure.
[0030] FIG. 1 is an illustration of an example solid-state battery
including a metal foam in accordance with various aspects of the
current technology;
[0031] FIG. 2 is a spectroscopy image of the metal foam;
[0032] FIG. 3 is an illustration of another example solid-state
battery including a metal foam and having a dual-layered
solid-state electrolyte in accordance with various aspects of the
current technology;
[0033] FIG. 4A is an illustration of an example bipolar solid-state
battery including a metal foam in accordance with various aspects
of the current technology;
[0034] FIG. 4B is an illustration of an example bipolar solid-state
battery including a metal foam and a dual-layered current collector
in accordance with various aspects of the current technology;
and
[0035] FIG. 5 is an illustration of an example solid-state battery
including a partial metal foam in accordance with various aspects
of the current technology.
[0036] Corresponding reference numerals indicate corresponding
parts throughout the several views of the drawings.
DETAILED DESCRIPTION
[0037] Example embodiments are provided so that this disclosure
will be thorough, and will fully convey the scope to those who are
skilled in the art. Numerous specific details are set forth such as
examples of specific compositions, components, devices, and
methods, to provide a thorough understanding of embodiments of the
present disclosure. It will be apparent to those skilled in the art
that specific details need not be employed, that example
embodiments may be embodied in many different forms and that
neither should be construed to limit the scope of the disclosure.
In some example embodiments, well-known processes, well-known
device structures, and well-known technologies are not described in
detail.
[0038] The terminology used herein is for the purpose of describing
particular example embodiments only and is not intended to be
limiting. As used herein, the singular forms "a," "an," and "the"
may be intended to include the plural forms as well, unless the
context clearly indicates otherwise. The terms "comprises,"
"comprising," "including," and "having," are inclusive and
therefore specify the presence of stated features, elements,
compositions, steps, integers, operations, and/or components, but
do not preclude the presence or addition of one or more other
features, integers, steps, operations, elements, components, and/or
groups thereof. Although the open-ended term "comprising," is to be
understood as a non-restrictive term used to describe and claim
various embodiments set forth herein, in certain aspects, the term
may alternatively be understood to instead be a more limiting and
restrictive term, such as "consisting of" or "consisting
essentially of." Thus, for any given embodiment reciting
compositions, materials, components, elements, features, integers,
operations, and/or process steps, the present disclosure also
specifically includes embodiments consisting of, or consisting
essentially of, such recited compositions, materials, components,
elements, features, integers, operations, and/or process steps. In
the case of "consisting of," the alternative embodiment excludes
any additional compositions, materials, components, elements,
features, integers, operations, and/or process steps, while in the
case of "consisting essentially of," any additional compositions,
materials, components, elements, features, integers, operations,
and/or process steps that materially affect the basic and novel
characteristics are excluded from such an embodiment, but any
compositions, materials, components, elements, features, integers,
operations, and/or process steps that do not materially affect the
basic and novel characteristics can be included in the
embodiment.
[0039] Any method steps, processes, and operations described herein
are not to be construed as necessarily requiring their performance
in the particular order discussed or illustrated, unless
specifically identified as an order of performance. It is also to
be understood that additional or alternative steps may be employed,
unless otherwise indicated.
[0040] When a component, element, or layer is referred to as being
"on," "engaged to," "connected to," or "coupled to" another element
or layer, it may be directly on, engaged, connected or coupled to
the other component, element, or layer, or intervening elements or
layers may be present. In contrast, when an element is referred to
as being "directly on," "directly engaged to," "directly connected
to," or "directly coupled to" another element or layer, there may
be no intervening elements or layers present. Other words used to
describe the relationship between elements should be interpreted in
a like fashion (e.g., "between" versus "directly between,"
"adjacent" versus "directly adjacent," etc.). As used herein, the
term "and/or" includes any and all combinations of one or more of
the associated listed items.
[0041] Although the terms first, second, third, etc. may be used
herein to describe various steps, elements, components, regions,
layers and/or sections, these steps, elements, components, regions,
layers and/or sections should not be limited by these terms, unless
otherwise indicated. These terms may be only used to distinguish
one step, element, component, region, layer or section from another
step, element, component, region, layer or section. Terms such as
"first," "second," and other numerical terms when used herein do
not imply a sequence or order unless clearly indicated by the
context. Thus, a first step, element, component, region, layer or
section discussed below could be termed a second step, element,
component, region, layer or section without departing from the
teachings of the example embodiments.
[0042] Spatially or temporally relative terms, such as "before,"
"after," "inner," "outer," "beneath," "below," "lower," "above,"
"upper," and the like, may be used herein for ease of description
to describe one element or feature's relationship to another
element(s) or feature(s) as illustrated in the figures. Spatially
or temporally relative terms may be intended to encompass different
orientations of the device or system in use or operation in
addition to the orientation depicted in the figures.
[0043] Throughout this disclosure, the numerical values represent
approximate measures or limits to ranges to encompass minor
deviations from the given values and embodiments having about the
value mentioned as well as those having exactly the value
mentioned. Other than in the working examples provided at the end
of the detailed description, all numerical values of parameters
(e.g., of quantities or conditions) in this specification,
including the appended claims, are to be understood as being
modified in all instances by the term "about" whether or not
"about" actually appears before the numerical value. "About"
indicates that the stated numerical value allows some slight
imprecision (with some approach to exactness in the value;
approximately or reasonably close to the value; nearly). If the
imprecision provided by "about" is not otherwise understood in the
art with this ordinary meaning, then "about" as used herein
indicates at least variations that may arise from ordinary methods
of measuring and using such parameters. For example, "about" may
comprise a variation of less than or equal to 5%, optionally less
than or equal to 4%, optionally less than or equal to 3%,
optionally less than or equal to 2%, optionally less than or equal
to 1%, optionally less than or equal to 0.5%, and in certain
aspects, optionally less than or equal to 0.1%.
[0044] In addition, disclosure of ranges includes disclosure of all
values and further divided ranges within the entire range,
including endpoints and sub-ranges given for the ranges.
[0045] Example embodiments will now be described more fully with
reference to the accompanying drawings.
[0046] The current technology pertains to solid-state batteries
(SSBs), for example bipolar solid-state batteries, that include a
metal foam material, for example as a current collector. Each
bipolar solid-state battery includes a plurality of solid-state
electroactive material particles and/or solid-state electrolyte
particles embedded within pores of a metal foam and one or more
current collector foils disposed on or adjacent to one or more
surfaces of the metal foam material.
[0047] Solid-state batteries may have a bipolar stacking design
comprising a plurality of bipolar electrodes where a first mixture
of solid-state electroactive material particles (and optional
solid-state electrolyte particles) is disposed on a first side of a
current collector film, and a second mixture of solid-state
electroactive material particles (and optional solid-state
electrolyte particles) is disposed on a second side of a current
collector film that is parallel with the first side. The first
mixture may include, as the solid-state electroactive material
particles, cathode material particles. The second mixture may
include, as solid-state electroactive material particles, anode
material particles. The solid-state electrolyte particles in each
instance may be the same or different.
[0048] Such bipolar solid-state batteries may be incorporated into
energy storage devices, like rechargeable lithium-ion batteries,
which may be used in automotive transportation applications (e.g.,
motorcycles, boats, tractors, buses, mobile homes, campers, and
tanks). The present technology, however, may also be used in other
electrochemical devices, including aerospace components, consumer
goods, devices, buildings (e.g., houses, offices, sheds, and
warehouses), office equipment and furniture, and industrial
equipment machinery, agricultural or farm equipment, or heavy
machinery, by way of non-limiting example. In various aspects, the
present disclosure provides a rechargeable lithium-ion battery that
exhibits high temperature tolerance, as well as improved safety and
superior power capability and life performance.
[0049] An exemplary and schematic illustration of an
all-solid-state electrochemical cell unit (also referred to as "the
solid-state battery", "the solid-state battery cell unit", "the
battery cell unit", and/or "the battery") 20 that cycles lithium
ions is shown in FIG. 1. The battery 20 includes a negative
electrode (i.e., anode) 22, positive electrode (i.e., cathode) 24,
and a solid-state electrolyte layer 26. The negative electrode 22
and the positive electrode 24 are each disposed on or embedded
within a porous material 100A, 100B (e.g., metal foam),
respectively.
[0050] Though the illustrated example includes a single positive
electrode (i.e., cathode) 24 and a single negative electrode (i.e.,
anode) 22, the skilled artisan will recognize that the current
teachings apply to various other configurations, including those
having one or more cathodes and one or more anodes, as well as
various current collectors (i.e., metal foam) and current collector
films with electroactive particle layers disposed on or adjacent to
or embedded within one or more surfaces thereof. Likewise, it
should be recognized that the battery 20 may include a variety of
other components that, while not depicted here, are nonetheless
known to those of skill in the art. For example, the battery 20 may
include a casing, a gasket, terminal caps, and any other
conventional components or materials that may be situated within
the battery 20, including between or around the negative electrode
22, the positive electrode 24, and/or the solid-state electrolyte
26 layer.
[0051] The battery 20 can generate an electric current (indicated
by arrows in FIG. 1) during discharge by way of reversible
electrochemical reactions that occur when the external circuit 40
is closed (to connect the negative electrode 22 and the positive
electrode 24) and when the negative electrode 22 has a lower
potential than the positive electrode. The chemical potential
difference between the negative electrode 22 and the positive
electrode 24 drives electrons produced by a reaction, for example,
the oxidation of intercalated lithium, at the negative electrode 22
through the external circuit 40 towards the positive electrode 24.
Lithium ions, which are also produced at the negative electrode 22,
are concurrently transferred through the solid-state electrolyte
layer 26 towards the positive electrode 24. The electrons flow
through the external circuit 40 and the lithium ions migrate across
the solid-state electrolyte layer 26 to the positive electrode 24,
where they may be plated, reacted, or intercalated. The electric
current passing through the external circuit 40 can be harnessed
and directed through the load device 42 (in the direction of the
arrows) until the lithium in the negative electrode 22 is depleted
and the capacity of the battery 20 is diminished.
[0052] The battery 20 can be charged or reenergized at any time by
connecting an external power source (e.g., charging device) to the
battery 20 to reverse the electrochemical reactions that occur
during battery discharge. The external power source that may be
used to charge the battery 20 may vary depending on the size,
construction, and particular end-use of the battery 20. Some
notable and exemplary external power sources include, but are not
limited to, an AC-DC converter connected to an AC electrical power
grid though a wall outlet and a motor vehicle alternator. The
connection of the external power source to the battery 20 promotes
a reaction, for example, non-spontaneous oxidation of intercalated
lithium, at the positive electrode 24 so that electrons and lithium
ions are produced. The electrons, which flow back toward the
negative electrode 22 through the external circuit 40, and the
lithium ions, which move across the solid-state electrolyte 26 back
toward the negative electrode 22, reunite at the negative electrode
22 and replenish it with lithium for consumption during the next
battery discharge cycle. As such, a complete discharging event
followed by a complete charging event is considered to be a cycle,
where lithium ions are cycled between the positive electrode 24 and
the negative electrode 22.
[0053] The size and shape of the battery 20 may vary depending on
the particular applications for which it is designed.
Battery-powered vehicles and hand-held consumer electronic devices
are two examples where the battery 20 would most likely be designed
to different size, capacity, voltage, energy, and power-output
specifications. The battery 20 may also be connected, for example
in series, with other similar lithium-ion cells or batteries to
produce a greater voltage output, energy, and power if it is
required by the load device 42. The battery 20 can generate an
electric current to the load device 42 that can be operatively
connected to the external circuit 40. The load device 42 may be
fully or partially powered by the electric current passing through
the external circuit 40 when the battery 20 is discharging. While
the load device 42 may be any number of known electrically-powered
devices, a few specific examples of power-consuming load devices
include an electric motor for a hybrid vehicle or an all-electric
vehicle, a laptop computer, a tablet computer, a cellular phone,
and cordless power tools or appliances, by way of non-limiting
example. The load device 42 may also be an electricity-generating
apparatus that charges the battery 20 for purposes of storing
electrical energy.
[0054] With renewed reference to FIG. 1, the solid-state
electrolyte layer 26 acts as a separator that physically separates
the negative electrode 22 from the positive electrode 24. The
solid-state electrolyte layer 26 may be composed of a first
plurality of solid-state electrolyte particles 30. A second
plurality of solid-state electrolyte particles 90 may be mixed with
negative solid-state electroactive particles 50 in the negative
electrode 22, and a third plurality of solid-state electrolyte
particles 92 may be mixed with positive solid-state electroactive
particles 60 in the positive electrode 24, to form a continuous
electrolyte network, which may be a continuous lithium-ion
conduction network. For example, the negative solid-state
electroactive particles 50 and the positive solid-state
electroactive particles 60 are independently mixed with the
second/third plurality of solid-state electrolyte particles 90,
92.
[0055] The negative electrode 22 may be formed from a lithium host
material that is capable of functioning as a negative terminal of a
lithium-ion battery. For example, in certain variations, the
negative electrode 22 may be defined by a plurality of the negative
solid-state electroactive particles 50. In certain instances, as
illustrated, the negative electrode 22 is a composite comprising a
mixture of the negative solid-state electroactive particles 50 and
the second plurality of solid-state electrolyte particles 90. For
example, the negative electrode 22 may include greater than or
equal to about 30 wt. % to less than or equal to about 98 wt. %,
and in certain aspects, optionally greater than or equal to about
50 wt. % to less than or equal to about 80 wt. %, of the negative
solid-state electroactive particles 50 and greater than or equal to
about 0 wt. % to less than or equal to about 50 wt. %, and in
certain aspects, optionally greater than or equal to about 10 wt. %
to less than or equal to about 30 wt. %, of the second plurality of
solid-state electrolyte particles 90.
[0056] The second plurality of solid-state electrolyte particles 90
may be the same as or different from the first plurality of
solid-state electrolyte particles 30. In certain variations, the
negative electrode 22 may be a carbonaceous anode and the negative
solid-state electroactive particles 50 may comprise one or more
negative electroactive materials such as graphite, graphene, hard
carbon, soft carbon, and carbon nanotubes (CNTs). In other
variations, the negative solid-state electroactive particles 50 may
be lithium-based, for example, a lithium alloy. In still other
variations, the negative solid-state electroactive particles 50 may
be silicon-based comprising, for example, a silicon alloy and/or
silicon-graphite mixture. In still further variations, the negative
electrode 22 may comprise one or more negative electroactive
materials, such as lithium titanium oxide
(Li.sub.4Ti.sub.5O.sub.12); one or more metal oxides, such as
TiO.sub.2 and/or V.sub.2O.sub.5; and metal sulfides, such as FeS.
Thus, the negative solid-state electroactive particles 50 may be
selected from the group including, for example only, lithium,
graphite, graphene, hard carbon, soft carbon, carbon nanotubes,
silicon, silicon-containing alloys, tin-containing alloys, and
combinations thereof.
[0057] In certain variations, the negative electrode 22 may further
include one or more conductive additives. For example, the negative
solid-state electroactive particles 50 (and/or second plurality of
solid-state electrolyte particles 90) may be optionally
intermingled with one or more electrically conductive materials
(not shown) that provide an electron conduction path. The negative
electrode 22 may include greater than or equal to about 0 wt. % to
less than or equal to about 30 wt. %, and in certain aspects,
optionally greater than or equal to about 1 wt. % to less than or
equal to about 5 wt. %, of the one or more electrically conductive
additives. The negative electrode 22 may be substantially free of
insulating polymer binder materials, such as styrene-butadiene
rubber (SBR).
[0058] Electrically conductive materials may include, for example,
carbon-based materials or a conductive polymer. Carbon-based
materials may include, for example, particles of graphite,
acetylene black (such as KETCHEN.TM. black or DENKA.TM. black),
carbon fibers and nanotubes, graphene (such as graphene oxide),
carbon black (such as Super P), and the like. In certain aspects,
mixtures of the conductive additives materials may be used.
[0059] The positive electrode 24 may be formed from a lithium-based
or electroactive material that can undergo lithium intercalation
and deintercalation while functioning as the positive terminal of
the battery 20. For example, in certain variations, the positive
electrode 24 may be defined by a plurality of the positive
solid-state electroactive particles 60. In certain instances, as
illustrated, the positive electrode 24 is a composite comprising a
mixture of the positive solid-state electroactive particles 60 and
the third plurality of solid-state electrolyte particles 92. For
example, the positive electrode 24 may include greater than or
equal to about 30 wt. % to less than or equal to about 98 wt. %,
and in certain aspects, optionally greater than or equal to about
50 wt. % to less than or equal to about 80 wt. %, of the positive
solid-state electroactive particles 60 and greater than or equal to
about 0 wt. % to less than or equal to about 50 wt. %, and in
certain aspects, optionally greater than or equal to about 10 wt. %
to less than or equal to about 30 wt. %, of the third plurality of
solid-state electrolyte particles 92.
[0060] The third plurality of solid-state electrolyte particles 92
may be the same as or different from the first and/or second
pluralities of solid-state electrolyte particles 30, 90. In certain
variations, the positive electrode 24 may be one of a layered-oxide
cathode, a spinel cathode, and a polyanion cathode. For example, in
the instances of a layered-oxide cathode (e.g., rock salt layered
oxides), the positive solid-state electroactive particles 60 may
comprise one or more positive electroactive materials selected from
LiCoO.sub.2, LiNi.sub.xMn.sub.yCo.sub.1-x-yO.sub.2 (where
0.ltoreq.x.ltoreq.1 and 0.ltoreq.y.ltoreq.1),
LiNi.sub.xMn.sub.yAl.sub.1-x-yO.sub.2 (where 0.ltoreq.x.ltoreq.1
and 0.ltoreq.y.ltoreq.1), LiNi.sub.xMn.sub.1-xO.sub.2 (where
0.ltoreq.x.ltoreq.1), and Li.sub.1+xMO.sub.2 (where
0.ltoreq.x.ltoreq.1) for solid-state lithium-ion batteries. The
spinel cathode may include one or more positive electroactive
materials, such as LiMn.sub.2O.sub.4 and
LiNi.sub.xMn.sub.1.5O.sub.4(where 0.ltoreq.x.ltoreq.1). The
polyanion cation may include, for example, a phosphate, such as
LiFePO.sub.4, LiVPO.sub.4, LiV.sub.2(PO.sub.4).sub.3,
Li.sub.2FePO.sub.4F, Li.sub.3Fe.sub.3(PO.sub.4).sub.4, or
Li.sub.3V.sub.2(PO.sub.4)F.sub.3 for lithium-ion batteries, and/or
a silicate, such as LiFeSiO.sub.4 for lithium-ion batteries.
[0061] In various aspects, the positive solid-state electroactive
particles 60 may comprise one or more positive electroactive
materials selected from the group consisting of LiCoO.sub.2,
LiNi.sub.xMn.sub.yCo.sub.1-x-yO.sub.2 (where 0.ltoreq.x.ltoreq.1
and 0.ltoreq.y.ltoreq.1), LiNi.sub.xMn.sub.1-xO.sub.2 (where
0.ltoreq.x.ltoreq.1), Li.sub.1+xMO.sub.2 (where
0.ltoreq.x.ltoreq.1), LiMn.sub.2O.sub.4,
LiNi.sub.xMn.sub.1.5O.sub.4, LiFePO.sub.4, LiVPO.sub.4,
LiV.sub.2(PO.sub.4).sub.3, Li.sub.2FePO.sub.4F,
Li.sub.3Fe.sub.3(PO.sub.4).sub.4, Li.sub.3V.sub.2(PO.sub.4)F.sub.3,
LiFeSiO.sub.4, and combinations thereof. In certain aspects, the
positive solid-state electroactive particles 60 may be coated (for
example, by LiNbO.sub.3 and/or Al.sub.2O.sub.3) and/or the positive
electroactive material may be doped (for example, by aluminum
and/or magnesium). In still further variations, the positive
electrode 24 may be a low-voltage cathode and the positive
solid-state electroactive particles 60 may include one or more
positive electroactive materials, such as lithiated metal
oxide/sulfide (such as LiTiS.sub.2), lithium sulfide, sulfur, and
the like.
[0062] In certain variations, the positive electrode 24 may further
include one or more conductive additives. For example, the positive
solid-state electroactive particles 60 (and/or third plurality of
solid-state electrolyte particles 92) may be optionally
intermingled with one or more electrically conductive materials
(not shown) that provide an electron conduction path. The positive
electrode 24 may include greater than or equal to about 0 wt. % to
less than or equal to about 30 wt. %, and in certain aspects,
optionally greater than or equal to about 1 wt. % to less than or
equal to about 5 wt. %, of the one or more electrically conductive
additives. The positive electrode 24 may be substantially free of
insulating polymer binder materials, such as styrene-butadiene
rubber (SBR).
[0063] Electrically conductive materials may include, for example,
carbon-based materials or a conductive polymer. Carbon-based
materials may include, for example, particles of graphite,
acetylene black (such as KETCHEN.TM. black or DENKA.TM. black),
carbon fibers and nanotubes, graphene (such as graphene oxide),
carbon black (such as Super P), and the like. Examples of a
conductive polymer may include polyaniline, polythiophene,
polyacetylene, polypyrrole, and the like. In certain aspects,
mixtures of the conductive additives materials may be used.
[0064] The negative solid-state electroactive particles 50 and/or
the second plurality of solid-state electrolyte particles 90 (as
well as any additive) may be embedded within a metal foam 100A
and/or dispersed within the pores of the metal foam 100A, such that
the negative electrode 22 has a thickness (along the x-axis as
illustrated in FIG. 1) greater than or equal to about 100 .mu.m to
less than or equal to about 3000 .mu.m, and in certain aspects,
optionally greater than or equal to about 500 .mu.m to less than or
equal to about 2500 .mu.m.
[0065] Likewise, the positive solid-state electroactive particles
60 and/or the third plurality of solid-state electrolyte particles
92 (as well as any additive) may be embedded within a metal foam
100B and/or dispersed within the pores of the metal foam 100B such
that the positive electrode 24 has a thickness (along the x-axis as
illustrated in FIG. 1) greater than or equal to about 100 .mu.m to
less than or equal to about 3000 .mu.m, optionally greater than or
equal to about 200 .mu.m to less than or equal to about 2000 .mu.m,
optionally greater than or equal to about 200 .mu.m to less than or
equal to about 1000 .mu.m, and in certain aspects, optionally
greater than or equal to about 500 .mu.m to less than or equal to
about 1000 .mu.m
[0066] As illustrated in FIG. 2, the metal foams 100A, 100B are
porous material (i.e., pores 102) having a porosity greater than or
equal to about 80 vol. % to less than or equal to about 99 vol. %,
and in certain aspects, optionally greater than or equal to about
80 vol. % to less than or equal to about 95 vol. %. Metal foams
100A, 100B having porosities less than 80 vol. % may negatively
affect energy density levels, while metal foams 100A, 100B having
porosities greater than 95 vol. % will be fragile, as well as
expensive. The pores may have an average diameter greater than or
equal to about 2 .mu.m to less than or equal to about 5000 .mu.m,
and in certain aspects, optionally greater than or equal to about
100 .mu.m to less than or equal to about 1000 .mu.m.
[0067] The metal foams 100A, 100B may be the same or different.
Each metal foam 100A, 100B comprises at least one of aluminum (Al)
foam, nickel (Ni) foam, copper (Cu) foam, nickel-chromium (Ni--Cr)
foam, nickel-tin (Ni--Sn) foam, and titanium (Ti) foam. In certain
aspects, the metal foams 100A, 100B may be carbon or graphene
coated metal foams. The carbon or graphene coatings may improve the
corrosion resistance of the metal foams 100A, 100B. The metal foams
100A, 100B may have thicknesses (along the x-axis) greater than or
equal to about 100 .mu.m to less than or equal to about 3000 .mu.m,
and in certain aspects, optionally greater than or equal to about
500 .mu.m to less than or equal to about 2500 .mu.m. The metal
foams 100A, 100B may provide improved electronic paths and/or a
reduced internal resistance within the battery 20 so as to, for
example only, reduce resistive losses and promote power
capabilities within the battery 20.
[0068] Though a metal foam (e.g., metal foam 100A, 100B) is
discussed herethroughout it is understood that in each instance the
current technology also applies to other porous materials having a
porosity greater than or equal to about 80 vol. % to less than or
equal to about 99 vol. %, and in certain aspects, optionally
greater than or equal to about 80 vol. % to less than or equal to
about 95 vol. % and an average diameter greater than or equal to
about 2 .mu.m to less than or equal to about 5000 .mu.m, and in
certain aspects, optionally greater than or equal to about 100
.mu.m to less than or equal to about 1000 .mu.m, such as carbon
nanofiber three-dimensional foam, graphene foam, carbon cloth,
carbon fiber-embedded carbon nanotubes, carbon nanotubes
three-dimensional current collectors (such as, carbon nanotube
paper), graphene-nickel foam, and the like.
[0069] A negative electrode current collector foil 32 may be
positioned at or near the negative electrode 22. The negative
electrode current collector foil 32 may be formed from copper or
any other appropriate electrically conductive material known to
those of skill in the art. The negative electrode current collector
foil 32 may be a foil disposed on a top surface of the metal foam
100A. In such instances, the metal foam 100A provides support to
the negative electrode current collector foil 32 such that the
negative current collector foil 32 may have a thickness of less
than about 10 .mu.m. For example, the negative electrode current
collector foil 32 may have a thickness of greater than or equal to
about 2 .mu.m to less than or equal to about 30 .mu.m.
[0070] Likewise, a positive electrode current collector foil 34 may
be positioned at or near the positive electrode 24. The positive
electrode current collector foil 34 may be formed from aluminum or
any other electrically conductive material known to those of skill
in the art. The positive electrode current collector foil 34 may be
a foil disposed on a top surface of the metal foam 100B. In such
instances, the metal foam 100B provides support to the positive
electrode current collector foil 34 such that the positive current
collector foil 34 may have a thickness of less than about 10 .mu.m.
For example, the positive electrode current collector foil 34 may
have a thickness of greater than or equal to about 2 .mu.m to less
than or equal to about 30 .mu.m.
[0071] The negative electrode current collector foil 32 and the
positive electrode current collector foil 34 respectively collect
and move free electrons to and from an external circuit 40 (as
shown by the block arrows). For example, an interruptible external
circuit 40 and a load device 42 may connect the negative electrode
22 (through the negative electrode current collector 32) and the
positive electrode 24 (through the positive electrode current
collector 34).
[0072] With renewed reference to FIG. 1, the solid-state
electrolyte layer 26 provides electrical separation--preventing
physical contact--between the negative electrode 22 (i.e., an
anode) and the positive electrode 24 (i.e., a cathode). In various
aspects, the solid-state electrolyte layer 26 may be defined by a
first plurality of solid-state electrolyte particles 30 having, for
example, an average particle diameter greater than or equal to
about 100 nm to less than or equal to about 100 .mu.m. For example,
the solid-state electrolyte layer 26 may be in the form of a hot or
cold pressed layer or a composite that comprises the first
plurality of solid-state electrolyte particles 30, such as a
compact inorganic solid-state electrolyte layer. The solid-state
electrolyte layer 26 may be in the form of a layer having a
thickness (along the x-axis) greater than or equal to about 5 .mu.m
to less than or equal to about 100 .mu.m, and in certain aspects,
optionally about 30 .mu.m. In certain variations, the solid-state
electrolyte particles 30 may have an average diameter that is about
25% of the total average thickness of the solid-state electrolyte
26. The solid-state electrolyte layer 26 may have an interparticle
porosity greater than or equal to about 1 vol. % to less than or
equal to about 15 vol. %.
[0073] The solid-state electrolyte particles 30 may include one or
more sulfide-based particles, halide-based particles, hydride-based
particles, and the like. In still further variations, the
solid-state electrolyte particles 30 may comprise one or more
oxide-based particles. In each instance, as would be appreciated by
one of ordinary skill in the art, the solid-state electrolyte
particles 30 may be wetted by a small amount (for example, greater
than or equal to about 5 wt. % to less than or equal to about 20
wt. %) of a liquid electrolyte (e.g. Li.sub.7P.sub.3S.sub.11 may be
wetted by LiTFSI-Triethylene glycol dimethyl ether, an ionic liquid
electrolyte).
[0074] In certain variations, the sulfide-based particles may have
superionic conductivities (e.g., 10.sup.-4.about.10.sup.-2 S/cm).
The sulfide-based particles may include pseudobinary sulfides,
pseudoternary sulfides, and/or pseudoquaternary sulfides.
Pseudobinary sulfides include, for example only,
Li.sub.2S--P.sub.2S.sub.5 systems (such as Li.sub.3PS.sub.4,
Li.sub.7P.sub.3S.sub.11, Li.sub.9.6P.sub.3S.sub.12),
Li.sub.2S--SnS.sub.2 systems (such as Li.sub.4SnS.sub.4),
Li.sub.2S--SiS.sub.2 systems, Li.sub.2S--GeS.sub.2 systems,
Li.sub.2S--B.sub.2S.sub.3 systems, Li.sub.2S--Ga.sub.2S.sub.3
systems, Li.sub.2S--P.sub.2S.sub.3 systems, and
Li.sub.2S--Al.sub.2S.sub.3 systems. Pseudoternary sulfides include,
for example only, Li.sub.2O--Li.sub.2S--P.sub.2S.sub.5 systems,
Li.sub.2S--P.sub.2S.sub.5--P.sub.2O.sub.5 system,
Li.sub.2S--P.sub.2S.sub.5--GeS.sub.2 systems (such as
Li.sub.3.25Ge.sub.0.25P.sub.0.75S.sub.4,
Li.sub.10GeP.sub.2S.sub.12), Li.sub.2S--P.sub.2S--P.sub.2S--LiX
systems (where X is one of F, Cl, Br, and I) (such as
Li.sub.6PS.sub.5Br, Li.sub.6PS.sub.5Cl, Li.sub.7P.sub.2S.sub.8I,
Li.sub.4PS.sub.4I), Li2S--As2S5-SnS2 systems (such as
Li.sub.3.833Sn.sub.0.833As.sub.0.166S.sub.4),
Li.sub.2S--P.sub.2S.sub.5--Al.sub.2S.sub.3 systems,
Li.sub.2S--LiX--SiS.sub.2 (where X is one of F, Cl, Br, and I)
systems, 0.4LiI.0.6Li.sub.4SnS.sub.4, and
Li.sub.11Si.sub.2PS.sub.12. Pseudoquaternary sulfides include, for
example only, Li.sub.2O--Li.sub.2S--P.sub.2S.sub.5--P.sub.2O.sub.5
systems, Li.sub.9.54Si.sub.1.74P.sub.1.44S.sub.11.7Cl.sub.0.3,
Li.sub.7P.sub.2.9Mn.sub.0.1S.sub.10.7I.sub.0.3, and
Li.sub.10.35[Sn.sub.0.27Si.sub.1.08]P.sub.1.65S.sub.12. Solid-state
electrolytes, like solid-state electrolyte layer 26, including such
sulfide-based particles may be deformable, such that the
solid-state electrolyte particles can be consolidated at room
temperature without high-temperature sintering processes. Further
still, solid-state electrolytes, like solid-state electrolyte layer
26, including such sulfide-based particles may have a superionic
conductivity greater than or equal to about 10.sup.-7 S/Cm to less
than or equal to about 10.sup.-2 S/cm.
[0075] In certain variations, the halide-based particles may
include, for example only, Li.sub.3YCl.sub.6, Li.sub.3InCl.sub.6,
Li.sub.3YBr.sub.6, LiI, Li.sub.2CdCl.sub.4, Li.sub.2MgCl.sub.4,
Li.sub.2CdI.sub.4, Li.sub.2ZnI.sub.4, and Li.sub.3OCl.
[0076] In certain variations, the hydride-based particles may
include, for example only, LiBH.sub.4, LiBH.sub.4--LiX (where X is
one of Cl, Br, and I), LiNH.sub.2, Li.sub.2NH,
LiBH.sub.4--LiNH.sub.2, and Li.sub.3AlH.sub.6.
[0077] In certain variations, the oxide-based particles may
comprise, for example only, one or more garnet ceramics,
LISICON-type oxides, NASICON-type oxides, and Perovskite type
ceramics. For example, the garnet ceramics may be selected from the
group consisting of: Li.sub.7La.sub.3Zr.sub.2O.sub.12,
Li.sub.6.2Ga.sub.0.3La.sub.2.95Rb.sub.0.05Zr.sub.2O.sub.12,
Li.sub.6.85La.sub.2.9Ca.sub.0.1Zr.sub.1.75Nb.sub.0.25O.sub.12,
Li.sub.6.25Al.sub.0.25La.sub.3Zr.sub.2O.sub.12,
Li.sub.6.75La.sub.3Zr.sub.1.75Nb.sub.0.25O.sub.12,
Li.sub.6.75La.sub.3Zr.sub.1.75Nb.sub.0.25O.sub.12, and combinations
thereof. The LISICON-type oxides may be selected from the group
consisting of: Li.sub.2+2xZn.sub.1-xGeO.sub.4 (where
0<x.ltoreq.1), Li.sub.14Zn(GeO.sub.4).sub.4,
Li.sub.3+x(P.sub.1-xSi.sub.x)O.sub.4 (where 0<x<1),
Li.sub.3+xGe.sub.xV.sub.1-xO.sub.4 (where 0<x<1), and
combinations thereof. The NASICON-type oxides may be defined by
LiMM'(PO.sub.4).sub.3, where M and M' are independently selected
from Al, Ge, Ti, Sn, Hf, Zr, and La. For example, in certain
variations, the NASICON-type oxides may be selected from the group
consisting of: Li.sub.1+xAl.sub.xGe.sub.2-x(PO.sub.4).sub.3 (LAGP)
(where 0.ltoreq.x.ltoreq.2),
Li.sub.1.4Al.sub.0.4Ti.sub.1.6(PO.sub.4).sub.3,
Li.sub.1.3Al.sub.0.3Ti.sub.1.7(PO.sub.4).sub.3,
LiTi.sub.2(PO.sub.4).sub.3, LiGeTi(PO.sub.4).sub.3,
LiGe.sub.2(PO.sub.4).sub.3, LiHf.sub.2(PO.sub.4).sub.3, and
combinations thereof. The Perovskite-type ceramics may be selected
from the group consisting of: Li.sub.3.3La.sub.0.53TiO.sub.3,
LiSr.sub.1.65Zr.sub.1.3Ta.sub.1.7O.sub.9,
Li.sub.2x-ySr.sub.1-xTa.sub.yZr.sub.1-yO.sub.3 (where x=0.75y and
0.60<y<0.75),
Li.sub.3/8Sr.sub.7/16Nb.sub.3/4Zr.sub.1/4O.sub.3,
Li.sub.3xLa.sub.(2/3-x)TiO.sub.3 (where 0<x<0.25), and
combinations thereof.
[0078] In various aspects, as illustrated in FIG. 3, the present
disclosure provides another example solid-state battery 400. The
solid-state battery 400 may include a dual-layered solid-state
electrolyte 426. The dual-layered solid-state electrolyte 426 may
include parallel first and second solid-state electrolyte layers
426A, 426B. For example, as illustrated, the first solid-state
electrolyte layer 426A may be adjacent to or near a negative
electrode 422, and the second solid-state electrolyte layer 426B
may be adjacent to or near a positive electrode 424.
[0079] As in the instance of FIG. 1, the negative electrode 422 may
be formed from a lithium host material that is capable of
functioning as a negative terminal of a lithium-ion battery. For
example, in certain variations, the negative electrode 422 may be
defined by a plurality of the negative solid-state electroactive
particles 450. In certain instances, as illustrated, the negative
electrode 422 is a composite comprising a mixture of the negative
solid-state electroactive particles 450 and a third plurality of
solid-state electrolyte particles 490. Each of the negative
solid-state electroactive particles 450 and/or the third plurality
of solid-state electrolyte particles 490 may be disposed on or
embedded within a metal foam 400A. A negative electrode current
collector foil 432 may be positioned at or near the negative
electrode 422. The negative electrode current collector foil 432
may be formed from copper or any other appropriate electrically
conductive material known to those of skill in the art. The
negative electrode current collector foil 432 may be a foil
disposed on a top surface of the metal foam 400A.
[0080] Likewise, the positive electrode 424 may be formed from a
lithium-based or electroactive material that can undergo lithium
intercalation and deintercalation while functioning as a positive
terminal of a lithium-ion battery. For example, in certain
variations, the positive electrode 424 may be defined by a
plurality of the positive solid-state electroactive particles 460.
In certain instances, as illustrated, the positive electrode 424 is
a composite comprising a mixture of the positive solid-state
electroactive particles 460 and a fourth plurality of solid-state
electrolyte particles 492. Each of the positive solid-state
electroactive particles 460 and/or the fourth plurality of
solid-state electrolyte particles 492 may be disposed on or
embedded within a metal foam 400B. A positive electrode current
collector foil 434 may be positioned at or near the positive
electrode 424. The positive electrode current collector foil 434
may be formed from aluminum or any other electrically conductive
material known to those of skill in the art. The positive electrode
current collector foil 434 may be a foil disposed on a top surface
of the metal foam 400B.
[0081] With renewed reference to FIG. 3, the first solid-state
electrolyte layer 426A may be defined by a first plurality of
solid-state electrolyte particles 430A. The second solid-state
electrolyte layer 426B may be defined by a second plurality of
solid-state electrolyte particles 430B. In certain instances, the
first and second pluralities of solid-state electrolyte particles
430A, 430B may be the same--that is, the first solid-state
electrolyte layer 426A may be the same as (identical to) the second
solid-state electrolyte layer 426B. In other instances, the first
and second pluralities of solid-state electrolyte particles 430A,
430B may be different. The third plurality of solid-state
electrolyte particles 490 and/or the fourth plurality of
solid-state electrolyte particles 492 may be the same or different
as the first and second pluralities of solid-state electrolyte
particles 430A, 430B.
[0082] The pluralities of solid-state electrolyte particles 430A,
430B, 490, 492 may include those solid-state electrolyte materials
described in the context of FIG. 1. For example, the solid-state
electrolyte layers 426A, 426B may be compact inorganic solid-state
electrolyte layers. In other instances, the solid-state electrolyte
layers 426A, 426B may be hybrid electrolyte layers including an
organic component and/or an inorganic component.
[0083] The organic component may include one or more polymers and a
liquid electrolyte. The one or more polymers may be selected from
polyethylene glycol, poly(phenylene oxide) (PPO), poly(methyl
methacrylate) (PMMA), polyacrylonitrile (PAN), polyvinylidene
fluoride (PVDF), poly(vinylidene fluoride-co-hexafluoropropylene
(PVDF-HFP), polyvinyl chloride (PVC), polytetrafluoroethylene
(PTFE), carboxymethyl cellulose (CMC), styrene-butadiene (SBR),
acrylonitrile butadiene rubber (NBR),
poly(styrene-butadiene-styrene) (SBS), and combinations thereof.
The liquid electrolyte may be, for example only, one of lithium
bis(trifluoromethanesulfonyl)imide (LiTFSI)-triethylene glycol
dimethyl ether, lithium hexafluorophosphate (LiPF.sub.6)-ethylene
carbonate (EC), diethyl carbonate (DEC) with one or more additives
(such as vinylene carbonate (VC), fluoroethylene carbonate, vinyl
ethylene carbonate, lithium bis(oxalato) borate), and lithium
bis(trifluoromethanesulfonyl)imide (LiTFSI)-acetonitrile.
[0084] The inorganic component may include one or more
sulfide-based particles, halide-based particles, hydride-based
particles, oxide-based particles, and the like, as detailed above.
The inorganic component may also include one or more lithium salts,
such as lithium bis(trifluoromethanesulfonyl)imide (LiTFSI),
lithium hexafluorophosphate (LiPF.sub.6), lithium
bis(fluorosulfonyl)imide (LiFSI), and/or lithium tetrafluoroborate
(LiBF.sub.4). In still further variations, the inorganic component
may include one or more oxide ceramic nanoparticles, such as
silicon dioxide (SiO.sub.2), cerium dioxide (CeO.sub.2), aluminum
oxide (Al.sub.2O.sub.3), and/or zirconium dioxide (ZrO.sub.2).
[0085] Though the above illustrated examples (FIG. 1 and FIG. 3)
include a single positive electrode (i.e., cathode) 24, 424 and a
single negative electrode (i.e., anode) 22, 422, the skilled
artisan will recognize that the above teachings apply to various
other configurations, including those having one or more cathodes
and one or more anodes, as well as various current collectors with
electroactive particles layers disposed on or adjacent to one or
more surfaces thereof. For example, as illustrated in FIGS. 4A-4B,
a solid-state battery 500 may include a plurality of electrodes,
such as a first bipolar electrode 502A and a second bipolar
electrode 502B. The asterisks in FIGS. 4A-4B are meant to
illustrate that the battery 500 may include one or more additional
electrodes, as would be appreciated by the skilled artisan.
[0086] Each of the bipolar electrodes 502A, 502B includes a first
plurality of electroactive material particles 550 disposed adjacent
to or on a first side or surface 532 of a current collector 536 and
a second plurality of electroactive material particles 560 disposed
adjacent to or on a second side or surface 534 of the current
collector 536. As in the instance of FIG. 1, the first plurality of
electroactive material particles 550 and/or second plurality of
electroactive material particles 560 may be disposed on or embedded
within metal foams 598A, 598B, respectively. The first plurality of
electroactive material particles 550 may be negative solid-state
electroactive material particles, such as detailed above in the
context of negative solid-state electroactive particles 50. The
second plurality of electroactive material particles 560 may be
positive solid-state electroactive material particles, such as
detailed above in the context of positive solid-state electroactive
particles 60.
[0087] In certain variations, as illustrated, a first plurality of
solid-state electrolyte particles 590 may be mixed or intermingled
with the first plurality of electroactive material particles 550;
and a second plurality of solid-state electrolyte particles 592 may
be mixed or intermingled with the second plurality of electroactive
material particles 560. A solid-state electrolyte layer 526 may be
disposed between consecutive electrodes 502A, 502B. The solid-state
electrolyte layer 526 acts as a separator that physically separates
the first electrode 502A and the second electrode 502B. The
solid-state electrolyte layer 526 may be defined by a third
plurality of solid-state electrolyte particles 530. As in the
instance of FIG. 1, the first, second, and third pluralities of
electrolyte particles 550, 560, 530 may be the same or different.
The skilled artisan will also recognize that the solid-state
electrolyte layer 526 may be, in certain variations, a dual-layered
solid-state electrolyte, such as detailed in the context of FIG.
3.
[0088] With renewed reference to FIG. 4A, the current collector
foil 536 may be disposed on a (top) surface of the metal foam 598A
and/or 598B. The current collector foil 536 may have a thickness
greater than or equal to about 2 .mu.m to less than or equal to
about 30 .mu.m. The current collector foil 536 may include at least
one of stainless steel, aluminum, nickel, iron, titanium, copper,
tin, or any other electrically conductive material known to those
of skill in the art. In certain variations, the current collector
foil 536 may a cladded foil (i.e., where one side (e.g., first
side) of the current collector comprises one metal (e.g., first
metal) and another side (e.g., second side) of the current
collector comprises another metal (e.g., second metal)) including,
for example only, aluminum-copper (Al--Cu), nickel-copper (Ni--Cu),
stainless steel-copper (SS-Cu), aluminum-copper (Al--Ni),
aluminum-stainless steel (Al-SS), and nickel-stainless
steel(Ni-SS). In certain variations, the current collector foil 536
may be pre-coated, such as carbon-coated aluminum current
collectors.
[0089] In other variations, as illustrated in FIG. 4B, the current
collector foil 536 may include a first current collector foil 538
and a second current collector foil 542. The first and second
current collector foils 538, 542 may be disposed on a (top) surface
of the metal foam 598A and/or the metal foam 598B. For example, the
first current collector foil 538 may be disposed on a first metal
foam 598A, and the second current collector foil 542 may be
disposed on a second metal foam 598B. The first current collector
foil 538 may define the first side or surface 532 of the current
collector 536, and the second current collector 542 may define the
second side or surface 534 of the current collector 536. As such,
the first current collector foil 538 may be adjacent or near the
first plurality of electroactive material particles 550 (first
plurality of solid-state electrolyte particles 590) and the second
current collector foil 542 may be adjacent or near the second
plurality of electroactive material particles 560 (and second
plurality of solid-state electrolyte particles 592).
[0090] The first current collector foil 538 may be different from
the second current collector foil 542. In certain variations, the
first current collector foil 538 may be a negative electrode
current collector foil and the second current collector foil 542
may be a positive electrode current collector foil. In each
instance, the first and second current collector foils 538, 542 may
each comprise at least one of stainless steel, aluminum, nickel,
iron, titanium, copper, tin, or any other electrically conductive
material known to those of skill in the art. The first and second
current collectors foils 538, 542 may each have a thickness such
that the current collector 536 has a thickness greater than or
equal to about 2 .mu.m to less than or equal to about 30 .mu.m.
[0091] In various aspects, as illustrated in FIG. 5, the present
disclosure provides another example solid-state battery 600. The
solid-state battery 600 may include a metal foam 698 only in a
portion of the battery 600. For example, as illustrated, a positive
electrode (i.e., cathode) 624 may include a metal foam 698. The
negative electrode (i.e., anode) 622 may be free of a metal foam
698. A solid-state electrolyte layer 626 disposed between the
positive electrode 624 and the negative electrode 622 may also be
free of the metal foam 698. As in the above described instances,
the solid-state electrolyte layer 626 may be defined by a first
plurality of solid-state electrolyte particles 630. Though the
positive electrode 624 is illustrated as including the metal foam
698, the skill artisan will appreciate that in others instances a
positive electrode may be free of a metal foam, while a negative
electrode may include the metal foam.
[0092] As in the instance of FIG. 1, the negative electrode 622
(without the metal foam) may be formed from a lithium host material
that is capable of functioning as a negative terminal of a
lithium-ion battery. For example, in certain variations, the
negative electrode 622 may be defined by a plurality of the
negative solid-state electroactive particles 660. In certain
instances, as illustrated, the negative electrode 622 is a
composite comprising a mixture of the negative solid-state
electroactive particles 660 and a second plurality of solid-state
electrolyte particles 692. The negative electrode 622 may have a
first thickness of greater than or equal than about 100 .mu.m to
less than or equal to about 3000 .mu.m, and in certain instances,
optionally greater than or equal to about 500 .mu.m to less than or
equal to about 2500 .mu.m.
[0093] Likewise, the positive electrode 624 may be formed from a
lithium-based or electroactive material that can undergo lithium
intercalation and deintercalation while functioning as a positive
terminal of a lithium-ion battery. For example, in certain
variations, the positive electrode 624 may be defined by a
plurality of the positive solid-state electroactive particles 650.
In certain instances, as illustrated, the positive electrode 624 is
a composite comprising a mixture of the positive solid-state
electroactive particles 650 and a third plurality of solid-state
electrolyte particles 634. Each of the positive solid-state
electroactive particles 650 and/or the third plurality of
solid-state electrolyte particles 634 may be disposed on or
embedded within a metal foam 698. The positive electrode 624 may
have a second thickness that is greater than the first thickness of
the negative electrode 622. For example, the positive electrode 624
may have a thickness greater than or equal than about 100 .mu.m to
less than or equal to about 2000 .mu.m, and in certain instances,
optionally greater than or equal to about 500 .mu.m to less than or
equal to about 1500 .mu.m. The metal foam 698 reduces internal
resistance and enables the greater thickness of the positive
electrode 624.
[0094] A current collector foil 632A may be positioned at or near
the negative electrode 622. Another current collector foil 632B may
be positioned at or near the positive electrode 624. In each
instance, the current collector foils 632A, 632B may include at
least one of stainless steel, aluminum, nickel, iron, titanium,
copper, tin, or any other electrically conductive material known to
those of skill in the art. In certain variations, the current
collector foils 632A, 632B may include a cladded foil such as, for
example only, aluminum-copper (Al--Cu), nickel-copper (Ni--Cu),
stainless steel-copper (SS-Cu), aluminum-copper (Al--Ni),
aluminum-stainless steel (Al-SS), and nickel-stainless
steel(Ni-SS). In certain variations, the current collector foils
632A, 632B may be pre-coated, such as carbon-coated aluminum
current collectors.
[0095] Certain features of the current technology are further
illustrated in the following non-limiting example.
Example
[0096] An example cell is prepared in accordance with various
aspects of the present disclosure. For example, the example cell
may include a positive electrode (i.e., cathode) comprising about
70 wt. % of NMC622 as the positive solid-state electroactive
material. The positive solid-state electroactive material may be
disposed on a metal foam having a porosity of about 87 vol. %. The
positive electrode may have a thickness of about 1 mm. The example
cell may further include a negative electrode (i.e., anode)
comprising about 60 wt. % graphite as the negative solid-state
electroactive material. The negative solid-state electroactive
material may also be disposed on the metal foam. A solid-state
electrolyte (SSE) may be disposed between the positive electrode
and the negative electrode of the example cell. The solid-state
electrolyte may have a thickness of about 30 .mu.m. A first current
collector foil may be disposed near or adjacent to the positive
electrode, and a second current collector foil may be disposed near
or adjacent to the negative electrode. The first and second current
collector foils may each have a thickness of about 10 .mu.m.
[0097] A comparative cell is also prepared. The comparative cell
may include a positive electrode (i.e., cathode) that also
comprises about 70 wt. % of NMC622 as the positive solid-state
electroactive material. The positive electrode may have a thickness
of about 100 .mu.m. The comparative cell may further include a
negative electrode (i.e., anode) comprising about 60 wt. % graphite
as the negative solid-state electroactive material. The negative
electrode may have a thickness of about 123 .mu.m. A solid-state
electrolyte (SSE) may be disposed between the positive electrode
and the negative electrode of the comparative cell. The solid-state
electrolyte may have a thickness of about 30 .mu.m. A first current
collector may be disposed near or adjacent to the positive
electrode, and a second current collector may be disposed near or
adjacent to the negative electrode. The first and second current
collector may each have a thickness of about 10 .mu.m.
[0098] The example cell may have an energy density of about 203
Wh/kg. The comparative cell may have an energy density of about 211
Wh/kg. The example exhibits a better charge/discharge rate
capability due to the sufficient electronic conduction and low
resistance within the electrode.
[0099] The foregoing description of the embodiments has been
provided for purposes of illustration and description. It is not
intended to be exhaustive or to limit the disclosure. Individual
elements or features of a particular embodiment are generally not
limited to that particular embodiment, but, where applicable, are
interchangeable and can be used in a selected embodiment, even if
not specifically shown or described. The same may also be varied in
many ways. Such variations are not to be regarded as a departure
from the disclosure, and all such modifications are intended to be
included within the scope of the disclosure.
* * * * *